Method of preparing chlorosulfuric esters of chlorinated alcohols



Patented July 27, 1954 UNITED PATENT OFFICE.

' Me'rnonorrnnmn ESTER-,8 F- on o ING CHLOROSULFURIC' RINATED ALCOHOLSMarcel Jean Viard, Bois-Golombcs, France, as-

onyn c dos Manufactures Ides.- Glaces ct Prod'uits Chimiqucs de Saint-Gobain, Chauny a. Cirey, Paris, France NoDrawing... Application April12, 1951, Serial No. 220,709

Claimspriority, application France April 18, 19,50

signor to Socicte An This invention relates to a process of makingchlorosulfuric esters of chlorinated alcohols.

The raw materials employed in this case are of the type described incopendingapplication- Serial No. 133,215, filed December 15, 1949. Theyare the complexes formed by thereaction of S02 on epoxides, and are ofdeterminate constitution but occur in several isometric forms. Forinstance, the reaction of S0 on ethylene oxide produces a series ofcompounds having the following formulas.

032 %O I O=S C O CH2-O S=O Called glycol sulflte. CHz-O (CHzCHzSOOnCalled polymeric glycolsulfite.

Which is an oxonium compound.

A method of making such compounds is set forth in that specification,which may be referred to for details. It is disclosed in thatapplication reaction of S02 on derivatives of the epoxides of' Theywhich epichlorhydrine is representative. compounds are generally calledcomplexes, of epoxides and sulfur dioxide, in this specification.

The process is carried out by chlorinating these complexes, eithersingly or together.

The objects of this invention are carried out, in the preferred form ofthe invention, by chlorinating such sulfldic complexes. The productsresulting from this chlorination reaction are the chlorosulfuric estersof chloroalkyl alcohols. For instance, by chlorinating the complex ofethylene oxide one obtains the chlorosulfuric ester of beta chlorethylalcohol, following the reaction 7 Claims.. (Cl. 260-456) There are threeraw materials which may be used to produce this compound, namely the' ply mer ofgly'col' sulfite, the monomer of glycol sul fite and theoxonium compound shown hereinabove. Upon chlorination they all appear toyield the identical product, as indicated in the.

examples which follow.

In practice one passes a current of chlorine gas through the rawmaterial, while keeping the mass at a temperature about 15C. orpreferably therebelow. This temperature is maintained" by refrigerationof any satisfactory type. The reaction may be stopped as soon as thestoichiometric quantity of chlorine has been. fixed in the raw material.but the flow of chlorine may be continued after that quantity has beenadded,

without inconvenience,v because there is no apparent danger, under theoperating conditions, of

fixing additional chlorine in the molecule of the chlorosulfuric esterthat is formed.

The speed of the reaction maybe accelerated? by means of a chlorinationcatalyst and the presence of a chlorination catalyst also has the eliectof improving the yield by eliminating secondary reactions. Camphor is anexcellent catalyst,.and ultraviolet light is also very useful. Theliquid products of reaction can be purified by distillation, which inthe case of the ester of ethyl alcohol, should be at reduced pressure.

Example I 108 grams of the polymer of glycol sulflte were: admitted to aballoon flask provided with an agi; tator. Through the liquid mass-therewaspassed a current of chlorine while the'temperature'was maintained-atabout 15 C. byexterior cooling, of:

the. flask.v Agitation continued throughout the reaction. The mass wasvery viscous at the be ginningofthe chlorination. but presently divided.itself into two layers, one of which was viscous;

and the other more fluid. As the absorption of chlorine continued themore fluid layer increased in volume and the viscous layer decreaseduntil finally there was obtained ahomogeneous liquid. The chlorinationwas stopped after 71 to '75 grams of chlorine had been admitted and theproduct was distilled under a vacuum of 18 of mercury. The productobtained was 95 to 1 10 grams of the chlorosulfuric ester of betachlorethyl alcohol. This material boiled at 95 C. at 18 mm. of pressure.The yield was about Example II 108 grams of the oxonium derivative ofthe formula shown hereinabove was admitted to the balloon flask used inExample I, with 1 gram of camphor. The flask was chilled to 5 to 10 C.during the operation and a current of chlorine was passed through theoxonium compound with agitation. When the mass had increased '75 gramsin weight the introduction of chlorine was stopped and the mass wasallowed to attain normal temperature. Thereafter, it was fractionated ina fractionating column by distillation at 18 mm. of mercury pressure.There was obtained 150l60 grams of the chlorosulfuric ester of betachlorethyl alcohol, substantially identical with that which is describedin Example I, in a yield representing 84 to 89%. The increase in theyield with respect to Example I was largely due to the presence ofcamphor as a catalyst.

Example III Into a simliar balloon flask there was admitted 216 grams ofmonomeric glycol sulfite. The flask was maintained between and 10 C.,with agitation, and a current of chlorine was passed through the mass.When the mass has increased 150 grams in weight the passage of chlorinewas discontinued, between 8 and 10' hours having elapsed. By exposingthe reaction mass to ultraviolet light throughout the reaction the timeof reaction was reduced from 8-10 hours to -6 hours. The raw productobtained weighed between 330 and 340 grams and was the samechlorosuliuric ester described above. The yield, using ultravioletlight, was between 92 and 95%.

From the foregoing three examples, it is observable that the three rawmaterials, the oxonium compound, monomeric glycol sulfite and polyglycolsulfite all yielded the same compound upon chlorination.

When the complexes produced from epichlorohydrine by reaction withsulfur dioxide are submitted to the identical process there is obtainedthe chlorosulfuric ester of dichloro-2-3 propylalcohol which has thefollowing formula:

01 CH: CH CH2 0 S0: Cl

The invention may be summarized as follows:

A process of making chlorosulfuric esters of chlorinated alcohols whichincludes the use, as raw materials, of the sulfidic complexes derivedfrom compositions containing the epoxy group by reaction with sulfurdioxide. In this invention such materials are chlorinated. The inventionalso involves the control of the reaction conditions by the maintenanceof a temperature preferably below 15 C, by the use of typicalchlorination catalysts and particularly by the use of camphor andultraviolet light as catalysts.

The chlorosulfuric esters of beta chloroethyl alcohol are of substantialimportance and constitute a preferred class of compounds produced by thenew process.

The chlorosulrurlc esters of chlorinated aliphatic alcohols are usefulas intermediates for further organic reactions.

As many apparently widely different embodiments of the present inventionmay be made without departing from the spirit and scope thereof, it isto be understood that the invention is not limited to thespecificembodiments.

What is claimed is:

1. The method of preparing a chlorosulfuric ester of a chlorinatedalcohol that consists essentially in passing a current of chlorinethrough a pool containing about 108 parts polyglycolsulfite at atemperature of about 15 C. with agitation until about '71-'75 partschlorine have been absorbed, and distilling the product at about 18 mm.Hg pressure.

2. The method of preparing a chlorosulfuric ester of a chlorinatedalcohol that consists essentially in passing a current of chlorinethrough a pool containing about 108 grams of the oxonium compound formedby the reaction of ethylene oxide and S02 in the presence of camphor ata temperature circa 5-10 C. until about grams C12 has been absorbed, andfractionally distilling the product at 18 mm. of Hg pressure.

3. The method of preparing a chlorosulfuric ester of a chlorinatedalcohol that consists essentially in passing a current of chlorinethrough a pool containing about 216 grams glycol sulfite at atemperature circa 0-10 C. in the presence of ultraviolet light untilgrams have been absorbed and fractionally distilling the product.

4. The method of preparing a chlorosulfuric ester of a chlorinated alkylalcohol that comprises reacting chlorine with a sulfidic complex formedby the reaction of sulfur dioxide on a member of the group consisting ofethylene oxide, the higher homologues thereof, and their chlorinatedsubstitution derivatives, at a temperature not materially higher than 15C.

5. The process of claim 4 in which the chlorination is carried out inthe presence of a chlorination catalyst.

6. The method of claim 5 in which the catalyst is camphor.

7. The method of claim 4 in which the chlorination is carried out in thepresence of ultraviolet light.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,497,135 Myles et a1. -1 Feb. 14, 1950 2,576,138 PechukasNov. 27, 1951 OTHER REFERENCES Chemical Abstracts, vol. 42 (1948) page2229, abstract of publication by Malinovski.

1. THE METHOD OF PREPARING A CHLOROSULFURIC ESTER OF A CHLORINATEDALCOHOL THAT CONSISTS ESSENTIALLY IN PASSING A CURRENT OF CHLORINETHROUGH A POOL CONTAINING ABOUT 108 PARTS POLYGLYCOLSULFITE AT ATEMPERATURE OF ABOUT 15* C. WITH AGITATION UNTIL ABOUT 71-75 PARTSCHLORINE HAVE BEEN ABSORBED, AND DISTILLING THE PRODUCT AT ABOUT 18 MM.HG PRESSURE.